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H and D photofragments produced via vibrationally mediated photodissociation of jet-cooled normal ethene (C2H4), 1,2-trans-d2-ethene (HDCCDH), and 1,1-d2-ethene (CH2CD2), initially excited to the fourth C–H stretch overtone region, were studied for the first time. H and D vibrational action spectra and Doppler profiles were measured. The action spectra include partially resolved features due to rotational cooling, while the monitored room temperature photoacoustic spectra exhibit only a very broad feature in each species. Simulation of the spectral contours allowed determination of the band types and origins, limited precision rotational constants, and linewidths, providing time scales for energy redistribution. The H and D Doppler profiles correspond to low average translational energies and show slight preferential C–H over C–D bond cleavage in the deuterated variants. The propensities toward H photofragments emerge even though the energy flow out of the initially prepared C–H stretch is on a picosecond time scale and the photodissociation occurs following internal conversion, indicating a more effective release of the light H atoms. [ABSTRACT FROM AUTHOR]

Room-temperature photoacoustic (PA) spectra and jet-cooled action spectra of the first to third overtone regions of the ethyl C–H stretches in vapor phase 1-butyne, CH3CH2C=C–H, were measured. Both the PA and action spectra exhibit a complex multiple peak structure being better resolved and more pronounced in the latter, due to inhomogeneous structure reduction. The observed manifolds were analyzed in terms of a simplified joint local-/normal-mode (LM/NM) model accounting for two types of C–H stretches (methyl and methylene) and for Fermi resonances between stretches and deformations. The retrieved parameters, used for calculation of the eigenstates, come from the best-fit parameters based on the diagonalization of the vibrational Hamiltonian in the LM/NM basis. The parameters were obtained by comparing the eigenvalues and the sum of the squares of the expansion coefficients of the eigenvectors of the C–H stretches of methyl and methylene to the action spectra peak positions and intensities, respectively. This approximate model vibrational Hamiltonian is proposed to explain most observed spectral features, corresponding to C–H stretch bands and to combinations of C–H stretches and deformations, indicating the importance of the Fermi resonance. The model was also applied to calculate the dynamics of the C–H stretching modes resulting from coupling with the deformations, implying rapid initial state decay on subpicosecond time scale. Decays of several picoseconds were found for complete transfer of probability from the initially prepared state of methylene and methyl to the counterpart LM states. [ABSTRACT FROM AUTHOR]

Vibrationally mediated photodissociation and photoacoustic (PA) spectroscopy were employed for studying the intramolecular dynamics of propyne initially excited to the first through fourth overtone of methyl C–H stretching modes. Room-temperature PA and jet-cooled action spectra, monitoring the absorption of the parent and the yield of the ensuing H photofragments, respectively, were obtained. The PA spectra exhibit mainly broad features, while the action spectra, due to inhomogeneous structure reduction, expose multiple peaks of recognizable shapes in the differing overtone manifolds. Symmetric rotor simulations of the band contours of the action spectra allowed retrieving of band origins and linewidths. The linewidths of the bands in each manifold enabled estimates for energy redistribution times out of the corresponding states to the bath states, the times ranging from 18±6 ps for two quanta of C–H excitation to subpicosecond for five quanta. The data were also analyzed in terms of a normal-mode model and a joint local-/normal-mode model. These models enabled determination of harmonic frequencies, anharmonicities, and interaction parameters reproducing the observed data in all monitored regions and provided spectral assignments. The measured Doppler profiles were well fitted by Gaussians with widths suggesting low average translational energies for the released H photofragments. These low energies and their similarities to those for dissociation of propyne isotopomers preexcited to acetylenic C–H stretches were ascribed to an indirect dissociation process occurring after internal conversion to the ground electronic state and isomerization to allene. [ABSTRACT FROM AUTHOR]